Novel bis(aryloxyalkyl) esters of aromatic polycarboxylic acids and method of preparation

ABSTRACT

The invention provides a compound of the formula: 
     
       
         
         
             
             
         
       
     
     wherein Ar is selected from the group consisting of aryl, monosubstituted aryl and poly-substituted aryl, heteroaryl, monosubstituted heteroaryl and polysubstituted heteroaryl; Ar′ is selected from the group consisting of aryl, monosubstituted aryl and polysubstituted aryl, heteroaryl, monosubstituted heteroaryl and polysubstituted heteroaryl; R is an alkylene radical having 2-20 carbon atoms; and n=1-20. The compounds of the invention are used with polymer resins to enhance their gas barrier properties.

This application claims the priority benefit under 35 U.S.C. section 119of U.S. provisional application Ser. No. 61/344,861 entitled “NovelCompositions and Method of Preparation” filed Oct. 26, 2010, which is inits entirety herein incorporated by reference. This application is alsoa continuation of U.S. Ser. No. 14/040,562 filed Sep. 27, 2013; now U.S.Pat. No. 9,409,852; which application is a continuation of U.S. pendingapplication Ser. No. 13/067,571 filed Jun. 9, 2011.

FIELD OF INVENTION

This invention relates to new and useful additives for enhancing the gasbarrier properties of polymeric resins and more in particular polyesterresins. The invention is also directed to a polymer composition andmethod for reducing the permeability of gases through molded polymericcontainers and films by incorporating into the polymer from which thecontainer or film is formed an effective amount of a barrier-enhancingadditive.

The invention further relates to a method for reducing gas permeabilityof shaped thermoplastic polymeric articles wherein the polymer fromwhich the article is formed is selected from the group consisting ofpolyesters, polycarbonates, polyetherimides and polyethersulfones byadding the novel additives of the invention.

The invention also provides improved polyethylene terephthalate resinformulations containing novel additives for improving resistance to gaspermeability.

The present invention is also directed to a polymer composition andmethod for improving the gas barrier performance of polymeric containersand films, and particularly containers for food and beverages which aremolded from thermoplastic polyester polymers.

The invention further relates to a polymer composition and method forreducing the permeability of gases through molded polymeric containers,sheets and films by incorporating into the polymer from which thecontainer, sheet or film is formed an effective amount of abarrier-enhancing additive of the type described herein.

The present invention also relates to polyester resins useful forforming packages for protecting comestibles. More specifically, itrelates to polyester resins for forming film and molding containerswhich have improved gas barrier properties.

The instant invention also relates to packages for protecting carbonatedbeverages and to the polyesters from which such packages are made. Morespecifically, it relates to films and molded containers which are formedfrom such polyesters.

The present invention further provides containers having improvedresistance to gas permeability. More specifically, the present inventionalso relates to a packaged beverage, and more particularly to enhancingthe carbon dioxide and oxygen barrier properties of a container for apackaged beverage, thereby increasing the shelf life of its contents, byincorporating an additive into polyethylene terephthalate (PET) and itscopolyesters.

BACKGROUND OF THE INVENTION

Formation of vessels such as drawn polyester bottles is very popular atthe present because they provide substantial weight advantage over glassbottles especially in shipping weight. These polyester vessels haveexcellent transparency and somewhat acceptable but not optimumgas-barrier properties, and they have been broadly used as vessels forliquid detergents, shampoos, cosmetics, and also for carbonated drinkssuch as beer, cola and soda pop and refreshing drinks such as fruitjuices and mineral water.

The drawn polyester bottles exhibit permeability to oxygen, carbondioxide gas and the like though the permeability is small, while the gaspermeability of completely sealed vessels such as glass bottles andmetal cans is substantially zero. Accordingly, drawn polyester bottlesare inferior to cans and glass bottles especially in the case ofcarbonated drinks, where loss of carbon dioxide gas occurs and there isa definite limit to the storage period.

Polyethylene terephthalate and its copolyesters (hereinafter referred tocollectively as “PET”) is the polyester of choice and is widely used tomake containers for carbonated soft drinks, juice, water, and the likedue to their excellent combination of clarity, mechanical, and somewhatacceptable gas barrier properties. In spite of these desirablecharacteristics, insufficient gas barrier of PET to oxygen and carbondioxide limits the application of PET for smaller sized packages, aswell as for packaging oxygen sensitive products, such as beer, juice,and tea products. A widely long felt need exists in the packagingindustry to further improve the gas barrier properties of PET.

The relatively high permeability of PET to carbon dioxide limits the useof smaller PET containers for packaging carbonated soft drinks. Thepermeation rate of carbon dioxide through PET containers is in the rangeof 3 to 14 cc's per day or 1.5 to 2 percent per week loss rate at roomtemperature depending on the size of the container. A smaller containerhas a larger surface area to volume ratio resulting in a higher relativeloss rate. For this reason, PET containers are currently used only aslarger containers for packaging carbonated soft drinks, while metal cansand glass containers are the choice for smaller carbonated soft drinkcontainers.

The amount of carbon dioxide that remains in a packaged carbonated softdrink determines its shelf life. Normally, carbonated soft drinkcontainers are filled with approximately four volumes of carbon dioxideper volume of water. It is generally accepted in the industry that apackaged carbonated soft drink reaches the end of its shelf life when17.5 percent of the carbon dioxide in the container is lost due topermeation of the carbon dioxide through the container side wall andclosure. The permeability of PET to carbon dioxide therefore determinesthe shelf life of the packaged carbonated beverage and thus, thesuitability of PET as a packaging material.

A wide variety of technologies have been developed or are beingdeveloped to enhance the barrier properties of PET to small gasmolecules. For example, external or internal coatings for enhancing thegas barrier of PET containers have been developed. The coating layer isnormally a very high barrier layer, either inorganic or organic, andslows down the diffusion of gases. Implementation of this technology,however, requires coating equipment not normally utilized in themanufacture of packaged beverages and therefore requires substantialcapital investment, increased energy usage, and increased floor space.In many beverage packaging plants that are already crowded, theadditional space is not an option.

Multi-layered containers have also been developed with a high barrierlayer sandwiched between two or more PET layers. Implementation of thistechnology also requires substantial capital investment and delaminationof the container layers impacts appearance, barrier, and mechanicalperformance of the containers.

A barrier additive for the PET or a polymer with inherent good barrierproperties would be good solutions that are welcomed by the industry.Neither such solution requires additional capital investment, andtherefore, does not have the limitations inherent with othertechnologies. A barrier additive can also be added during the injectionmolding process which gives more flexibility for downstream operations.

PET has been modified or blended with other components to enhance thegas barrier of the PET. Examples include polyethylene naphthalate(PEN)/PET copolymers or blends, isophthalate (IPA) modified PET, PETblended with polyethylene isophthalate (PEI) or a polyamide, such asnylon, and PET modified with resorcinol based diols. For a PET copolymerto achieve moderate barrier enhancement of 2× or higher, themodification is normally more than 10 to 20 weight or mole percent ofthe total co-monomers. When PET is modified to such a high level, thestretching characteristics of the PET are changed dramatically such thatthe normal PET container preform design could not be used in themanufacture of containers. Using these PET copolymers to moldconventional PET container preforms results in preforms that can not befully stretched and the ultimate containers are very difficult, if notimpossible, to make. Even if such a container can be made, it does notshow improved barrier performance and shows deteriorated physicalperformance such that it can not be used to package carbonated softdrinks.

Furthermore, PET blends with polyamide such as nylon developedyellowness and haze and are not clear like conventional PET.

Accordingly, there is a long felt need in the art to enhance the barrierperformance of PET for use in applications that will require enhancedbarrier properties, such as in the packaging of carbonated beverages andoxygen sensitive beverages and foods, in a manner that does not causesubstantial degradation of the PET, does not substantially impact thestretch ratio of the PET, and does not negatively impact the clarity ofthe PET.

Additionally, numerous examples of diesters of aromatic dicarboxylicacids have been disclosed in the prior art. For example,bis(hydroxyalkyl) esters of terephthalic and isophthalic acid areprecursors for the preparation of poly(alkylene)arylates such aspolyethylene terephthalate, polybutylene terphthalate, and polypropyleneterephthalate. Simple diesters of phthalic acid or phthalic anhydridesuch as bis(2-ethylhexyl) phthalate are widely known as being effectiveplasticizers for a variety of plastics. Diesters of aromaticdicarboxylic acids such as dimethylterephthalate, diethylterephthalateand diphenylterephthalate have been demonstrated to be useful as barrierenhancing additives in aromatic polyesters such as polyethyleneterephtahlate as disclosed in US patent application US 2006/0225568.Also, monoesters of hydroxybenzoic acid have also been disclosed thatfunction as plasticizers in aromatic polyesters WO/01/12521.

OBJECTS OF THE INVENTION

It is a first object of the present invention to provide novel additivesto improve the physical properties of polymeric formulations.

It is another object of the instant invention to provide novel additivesto improve the physical properties of polyester resins.

A further object of the invention is to provide novel additives forcopolyester resins.

A still further object of the invention is to provide novel additives toenhance the gas barrier properties of polymeric resins.

An additional object of the invention is to provide novel additives thatwhen blended with polyester resins enhance the shelf life of carbonatedbeverages.

A still further object of the invention is to provide polymeric shapedproducts containing the novel additives of the invention.

An additional object of the present invention are gas barrier enhancingadditives.

Still, another object of the invention are bis(aryloxylalkyl) esters ofaromatic dicarboxylic acids.

A further object of the invention is to provide gas barrier enhancingadditives base on bis(aryloxylalkyl) esters of aromatic dicarboxylicacids.

These and other objects of the present invention will more readilybecome apparent from the description and examples which follow.

SUMMARY OF THE INVENTION

The present invention and the inventive features described herein residein the discovery of certain barrier-enhancing additives forthermoplastic polymers. The invention is barrier enhancing additives anda polymer composition that contains one or more of the additives and amethod for reducing gas permeability of shaped polymeric articlesproduced from such a composition, such articles being generally selectedfrom containers, sheets and films.

Polymeric articles, and particularly extruded film or injection stretchblow molded polyester (e.g., PET) bottles, which contain one or more ofthe barrier-enhancing additives described herein, exhibit substantiallyreduced oxygen and carbon dioxide permeability values when measuredaccording to ASTM D3985 and water vapor permeability values whenmeasured according to ASTM F1249 in comparison to correspondingpolymeric articles which contained no barrier-enhancing additives.

The present invention provides a compound of the formula:

wherein Ar is selected from the group consisting of aryl,monosubstituted aryl and poly-substituted aryl, heteroaryl,monosubstituted heteroaryl and polysubstituted heteroaryl; Ar′ isselected from the group consisting of aryl, monosubstituted aryl andpolysubstituted aryl, heteroaryl, monosubstituted heteroaryl andpolysubstituted heteroaryl; R is an alkylene radical having 2-20 carbonatoms; and n=1-20.

The present invention is also directed to a method for making a compoundof the formula:

wherein Ar is selected from the group consisting of aryl,monosubstituted aryl and poly-substituted aryl, heteroaryl,monosubstituted heteroaryl and polysubstituted heteroaryl; Ar′ isselected from the group consisting of aryl, monosubstituted aryl andpolysubstituted aryl, heteroaryl, monosubstituted heteroaryl andpolysubstituted heteroaryl; R is an alkylene radical having 2-20 carbonatoms; and n=1-20; which method comprises:

-   reacting a compound of the formula

with a compound of the formula

Ar′—OR—O_(n)H

wherein Ar, Ar′, R and n are as defined above, at a temperature range ofabout 150° C. to about 275° C. in the presence of a color stabilizer fora sufficient time until the diester is formed.

The invention further provides a polymer composition comprising: (a) apolymer selected from the group consisting of polyesters,polycarbonates, polyetherimides and polyethersulfones including theirhomopolymers, random or block copolymers and a blend or blends of suchhomopolymers and copolymers; and (b) a gas barrier additive in effectiveamounts to reduce gas permeability having the formula

wherein Ar is selected from the group consisting of aryl,monosubstituted aryl and poly-substituted aryl, heteroaryl,monosubstituted heteroaryl and polysubstituted heteroaryl; Ar′ isselected from the group consisting of aryl, monosubstituted aryl andpolysubstituted aryl, heteroaryl, monosubstituted heteroaryl andpolysubstituted heteroaryl; R is an alkylene radical having 2-20 carbonatoms; and n=1-20.

The present invention also provides a method for reducing gaspermeability of shaped thermoplastic polymeric articles wherein thepolymer from which the article is formed is selected from the groupconsisting of polyesters, polycarbonates, polyetherimides andpolyethersulfones and wherein the method comprises the steps of: (1)incorporating into the polymer an amount of a barrier-enhancing additiveor a mixture of barrier-enhancing additives effective to reduce gaspermeability having the formula:

wherein Ar is selected from the group consisting of aryl,monosubstituted aryl and poly-substituted aryl, heteroaryl,monosubstituted heteroaryl and polysubstituted heteroaryl; Ar′ isselected from the group consisting of aryl, monosubstituted aryl andpolysubstituted 1 aryl, heteroaryl, monosubstituted heteroaryl andpolysubstituted heteroaryl; R is an alkylene radical having 2-20 carbonatoms; and n=1-20; and (2) shaping said polymeric articles.

The invention also provides a container comprising a polyestercomposition comprising a polyester and a gas barrier enhancing additive,wherein the gas barrier enhancing additive comprises a compound havingthe chemical structure of Formula II:

wherein X and X₆, independent of one another, comprise hydrogen, halide,heteroatom, hydroxyl, amino, amido, alkylamino, arylamino, alkoxy,aryloxy, nitro, acyl, cyano, sulfo, sulfato, mercapto, imino, sulfonyl,sulfenyl, sulfinyl, sulfamoyl, phosphonyl, phosphinyl, phosphoryl,phosphino, thioester, thioether, anhydride, oximno, hydrazino, carbamyl,phosphonic acid, phosphonato, or a C₁-C₁₀ monovalent hydrocarbon whichis unsubstituted or substituted with one or more functional moieties;wherein X₁, X₂, X₃, X₄, and X₅, independent of one another, comprise aheteroatom or a C₁-C₁₀ divalent hydrocarbon, wherein each heteroatom orC₁-C₁₀ divalent hydrocarbon is unsubstituted or substituted with one ormore functional moieties or one or more C₁-C₁₀ hydrocarbyls that areunsubstituted or substituted with one or more functional moieties; andwherein s, t, u, and v, independent of one another, is a number from 0to 10; wherein when X₃ comprises a C₆ or C₁₀ divalent aromatichydrocarbon, X and X₆, independent of one another, comprise a hydrogen,halide, heteroatom, hydroxyl, amino, amido, alkylamino, arylamino,alkoxy, aryloxy, nitro, acyl, cyano, sulfo, sulfato, mercapto, imino,sulfonyl, sulfenyl, sulfinyl, sulfamoyl, phosphonyl, phosphinyl,phosphoryl, phosphino, thioester, thioether, anhydride, oximno,hydrazino, carbamyl, phosphonic acid, phosphonato, or a C₃-C₁₀monovalent cyclic or heterocyclic non-aryl hydrocarbon that areunsubstituted or substituted with one or more functional moieties.

The invention also provides a polyester composition comprising apolyester and a gas barrier additive, wherein the gas barrier enhancingadditive comprises a compound having the chemical structure of FormulaII:

wherein X and X₆, independent of one another, comprise hydrogen, halide,heteroatom, hydroxyl, amino, amido, alkylamino, arylamino, alkoxy,aryloxy, nitro, acyl, cyano, sulfo, sulfato, mercapto, imino, sulfonyl,sulfenyl, sulfinyl, sulfamoyl, phosphonyl, phosphinyl, phosphoryl,phosphino, thioester, thioether, anhydride, oximno, hydrazino, carbamyl,phosphonic acid, phosphonato, or a C₁-C₁₀ monovalent hydrocarbon whichis unsubstituted or substituted with one or more functional moieties;wherein X₁, X₂, X₃, X₄, and X₅, independent of one another, comprise aheteroatom or a C₁-C₁₀ divalent hydrocarbon, wherein each heteroatom orC₁-C₁₀ divalent hydrocarbon is unsubstituted or substituted with one ormore functional moieties or one or more C₁-C₁₀ hydrocarbyls that areunsubstituted or substituted with one or more functional moieties; andwherein s, t, u, and v, independent of one another, is a number from 0to 10; wherein when X₃ comprises a C₆ or C₁₀ divalent aromatichydrocarbon, X and X₆, independent of one another, comprise a hydrogen,halide, heteroatom, hydroxyl, amino, amido, alkylamino, arylamino,alkoxy, aryloxy, nitro, acyl, cyano, sulfo, sulfato, mercapto, imino,sulfonyl, sulfenyl, sulfinyl, sulfamoyl, phosphonyl, phosphinyl,phosphoryl, phosphino, thioester, thioether, anhydride, oximno,hydrazino, carbamyl, phosphonic acid, phosphonato, or a C₃-C₁₀monovalent cyclic or heterocyclic non-aryl hydrocarbon that areunsubstituted or substituted with one or more functional moieties.

The invention further provides a shaped thermoplastic polymeric articlecomprising a base polymer having physically incorporated therein anamount of one or more barrier-enhancing additives effective to reducepermeability of the shaped article to gases when compared to the shapedarticle not having the one or more barrier-enhancing additivesincorporated therein, wherein the one or more barrier-enhancingadditives are selected from the group consisting of compounds of theformula:

wherein Ar is selected from the group consisting of aryl,monosubstituted aryl and poly-substituted aryl, heteroaryl,monosubstituted heteroaryl and polysubstituted heteroaryl; Ar′ isselected from the group consisting of aryl, monosubstituted aryl andpolysubstituted aryl, heteroaryl, monosubstituted heteroaryl andpolysubstituted heteroaryl; R is an alkylene radical having 2-20 carbonatoms; and n=1-20.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Applicant has found that the bis(aryloxylalkyl) esters of aromaticdicarboxylic acids such as terephthalic, isophthalic, andnapthalenedicarboxylic acids are novel and new compositions of matteruseful in barrier applications. Also, a simple and convenient process isdisclosed for their preparation.

In one embodiment, our invention relates to compounds of the formula:

wherein Ar is selected from the group consisting of aryl,monosubstituted aryl and poly-substituted aryl, heteroaryl,monosubstituted heteroaryl and polysubstituted heteroaryl; Ar′ isselected from the group consisting of aryl, monosubstituted aryl andpolysubstituted aryl, heteroaryl, monosubstituted heteroaryl andpolysubstituted heteroaryl; R is an alkylene radical having 2-20 carbonatoms; and n=1-20.

The aryl group in the compounds of formula (I) is selected from thegroup consisting of phenyl, naphthyl, biphenyl, terphenyl, and allpositional isomeric derivatives thereof. The mono and polysubstitutedaryl group of compounds of the formula (I) is selected from the groupconsisting of substituted phenyl, substituted naphthyl, substitutedbiphenyl, substituted terphenyl, and all positional isomeric derivativesthereof.

The substituent(s) in the aryl groups is selected from the groupconsisting of: —O⁽⁻⁾, —OH, —OR, —OC₆H₅, —OCOCH₃, —NH₂, —NR₂—NHCOCH₃—R,—C₆H₅, —NO₂, —NR₃ ⁽⁺⁾, —PR₃ ⁽⁺⁾, —SR₂ ⁽⁺⁾, —SO₃H, —SO₂R, —CO₂H, —CO₂R,—CONH₂, —CHO, —COR, —CN, —F, —Cl, —Br, —I, —CH₂Cl, and —CH═CHNO₂.

More specifically, the invention is directed to compounds of formula:

in which Ar is an arylene group such as terephthalyl, isophthalyl,naphthyl, and other aromatic moiety containing radicals, R is analkylene radical such as ethylene, propylene, isopropylene and butylene,and n is an integer between 1 and about 20. Ar′ is an arylene group orsubstituted arylene group such as terephthalyl, isophthalyl, naphthyl orother aromatic moiety containing radicals.

Compounds of formula (I) are derived from aromatic dicarboxylic acidsand aryloxyalkanols or substituted aryloxyalkanols of formula (II) inwhich Ar′ is an arlylene group or substituted

Ar′—OR—O_(n)H   (ii)

arylene group such as terepthalyl, isophthalyl, naphthyl and otheraromatic polycarboxylic acids and R is an alkylene radical such asethylene, propylene, isopropylene, butylenes, and C5-C18 alkylene and nis an integer from about 1 to about 20. Suitable compounds of formula(II) that are useful in the preparation of compounds of formula (I)include, but are not limited to alkoxylated phenol, alkoxylatednapthols, alkoxylated hydroxy biphenyls, and biphenyl ethers,alkoxylated styrenated phenols as well as their substituted derivatives.

Particular examples of compounds of formula (I) include the condensationproduct of terephthalic acid and 2-phenoxyethanol (iii);

the condensation product of terephthalic acid and ethoxylated 2-naphthol(iv);

the condensation product of terephthalic acid and ethoxylated 1-naphthol(v), and the analogous

and isophthalic and naphthalenedicarboxylic acid derivatives of theforegoing alcohols.

Regarding the method of preparation of the novel barrier additives ofthe invention, it is well known in the art that the synthesis of estersof aromatic mono and dicarboxylic acids often requires that the alcoholor glycol component be used in substantial excess. This is due to thelow solubility and high melting points of aromatic dicarboxylic acidssuch as terephthalic and isophthalic acids. The glycol or alcoholcomponent is used in excess in order to aid in the solubilization of theacid component, and also in order to drive the equilibriumesterification reaction to the desired ester. Esterification catalystsare also often necessary in order to achieve an acceptable reactionrate. In certain applications where aromatic esters have been used asadditives, such as food packaging and cosmetics, it is desirable for theadditive to be of high purity. It is therefore desirable to employ aprocess of preparation in which additional components such as catalystscan be minimized and in which the desired esters can be produced in highyield and in high purity.

The process of preparing the novel barrier additives of the inventionallows the synthesis of the compositions of formula (I) in high purityand yield without the use of a large excess of the alcohol or glycolether component, and without the use of conventional esterificationcatalysts that would have to be neutralized and filtered or somehowremoved from the reaction product. The reaction apparatus employed inthe synthesis of compositions of the present invention is representedschematically by FIG. 1. The apparatus consists of a conventionalesterification reactor that has been modified with a heated packedpartial condenser. The temperature of the partial condenser ismaintained above the boiling point of water and below the boiling of thealcohol or glycol ether reaction component thus allowing continuousreflux of the alcohol or glycol ether component while simultaneouslyremoving the water of esterification. The advantages of this method are:(1) Loss of alcohol or glycol ether in the water distillate is preventedmaking the use of a large excess of this component unnecessary, (2) Thewater of esterification is not contaminated with the alcohol or glycolether component negating a costly and time consuming separation. (3) Thefinal time required to vacuum strip the excess alcohol or glycol ethercomponent from the reaction mixture is greatly reduced. (4) The methodyields esters in high purity that are suitable as additives in foodcontact and cosmetic applications.

In a further embodiment, the present invention resides in the discoverythat oxygen, water vapor and carbon dioxide (CO2) permeability valuesfor shaped polymeric containers and films can be substantially reducedby incorporating into the base polymer from which the articles areformed effective amounts of a barrier-enhancing additive of the typedefined herein.

Suitable polyesters that can be compounded with the additives of theinvention are produced from the reaction of a diacid or diestercomponent comprising at least 65 mole % terephthalic acid or C₁-C₄dialkyl terephthalate, preferably at least 70 mole %, more preferably atleast 75 mole %, even more preferable at least 95 mole %, and aglycol/diol component comprising at least 65 mole % diol, preferably atleast 70 mole %, more preferably 75 mole %, even more preferably atleast 95 mole %. It is also preferable that the diacid component isterephthalic acid and the diol component is ethylene glycol. The molepercentage for all of the diacid component totals 100 mole %, and themole percentage for all of the diol component totals 100 mole %.

Where the polyester components are modified by one or more diolcomponents other than ethylene glycol, suitable diol components of thedescribed polyesters may be selected from the diols listed else whereherein, which diols include, for example, 1,2-propanediol;1,3-propane-diol; 1,4-butanediol; 2,2-dimethyl-1,3-propanediol;1,6-hexane-diol; 1,2-cyclohexane-diol; 1,4-cyclohexanediol;1,2-cyclohexanedimethanol; 1,3-cyclo-hexanedimethanol; and diolscontaining one or more oxygen atoms in the chain, for example,diethylene glycol, triethylene glycol, dipropylene glycol and similarglycols, and mixtures of all of the foregoing. In general, the diolscontain 2-18, preferably 2 to 8, carbon atoms. Cycloaliphatic diols canbe employed in their cis- or trans-forms, of as mixtures of both forms.Preferred modifying diol components are 1,4-cyclohexane-dimethanol ordiethylene glycol, or mixtures of thereof.

Where the polyester components are modified by one or more acidcomponents other than terephthalic acid, the suitable acid components(aliphatic, alicyclic or aromatic dicarboxylic acids) of the linearpolyester may be, for example, isophthalic acid,1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,succinic acid, glutaric acid, adipic acid, sebacic acid,1,12-dodecanedioic acid, 2,6-napthalenedicarboxylic acid, bibenzoicacid, and similar diacids, or mixtures thereof. In polymer preparationit is often preferred to use a functional derivative of the diacid, forexample, the dimethyl, diethyl, dipropyl and similar diester of thedicarboxylic acid. The anhydrides and acid halides of these diacids mayalso be used where practical.

Also, another contemplated polyester resin is a modified polyester madeby reacting at least 85 mole % terephthalate from either terephthalicacid or dimethyl terephthalate with any of the above co-monomers.

The polyesters of the present invention can be produced by any of theconventional methods of producing polyethylene terephthalate.Conventional methods of producing polyethylene terephthalate are wellknown and comprise reacting terephthalic acid with ethylene glycol at atemperature of about 200° C. to about 250° C. forming monomer and water.Because the reaction is reversible, the water is continuously removed,driving the reaction to the production of monomer. Next, the monomerundergoes a polycondensation reaction to form the polymer. During thereaction of the terephthalic acid and ethylene glycol it is notnecessary to have catalyst present. Generally, during thepolycondensation reaction, a catalyst is preferably present, forexample, an antimony catalyst or other catalyst known in the art. Whendiester are used in preparation of the polymer, other diacids and otherdiols may conventionally employed various catalysts as is well known inthe art.

The polyester composition of the invention typically has an I.V. fromabout 0.65 dL/g to about 1.0 dL/g.

Particularly useful polyester resins are the polyester resins sold byInvista (Spartanburg, S.C.). A resin designated as 1103 A isparticularly useful. Other resins that can be used include those listedin Table 1.

TABLE 1 Product Type Luster IV OxyClear ® Barrier Resin Copolymer Clear0.84 Polyclear ® PET 1101 Copolymer Clear 0.83 Polyclear ® PET 3300Copolymer Clear 0.72 Polyclear ® EBM PET Copolymer Clear 1 Polyclear ®PET T94N Copolymer Clear 0.87 PolyShield ® Resin Copolymer Clear 0.84

In accordance with a further preferred embodiment of the presentinvention, there is provided polymer compositions containing the gasbarrier additive in an amount in the range of about 0.05 to about 12weight percent of the polyester composition.

In a most preferred embodiment there is provided polyester compositionswherein the gas barrier additive is present in the polyester compositionin an amount in the range of about 0.05 to about 12 weight percent ofthe polyester composition.

The compositions of the invention are prepared by forming a uniformphysical blend, or mixture, comprising the base polymer and one or morebarrier-enhancing additives in the desired concentrations. As usedherein with reference to the invention, the term “composition” isintended to mean a physical blend or mixture. Water-sensitive basepolymers, such as, for example, polyesters should preferably bethoroughly dried by heating under air or nitrogen flow or vacuum asknown to those experienced in the art. The mixture is then heated andextruded or molded at a sufficiently high temperature to melt the basepolymer and provide for sufficient mixing of the additive or mixture ofadditives within the base polymer matrix. By way of example using PET,such melt temperature ranges from about 255° C. to 300° C. Thecomposition thus produced comprises the barrier-enhancing additive (ormixture of such additives) substantially in its (their) originalmolecular form; that is, only small amounts of barrier-enhancingadditive have been observed to react with the base polymer viatrans-esterification or other reaction mechanism typical of thefunctional groups present. It is preferred to prepare and extrude ormold the polymer composition under conditions of relatively lowtemperature and processing residence time which thereby minimizes theopportunity for the barrier-enhancing additives to react with the basepolymer. Best performance in terms of desirable mechanical properties ofpolymeric containers and films produced according to the invention isachieved when no more than about 10% of the gas barrier-enhancingadditive has reacted with the base polymer. As a consequence of anyreaction of a gas barrier-enhancing additive within the scope of theinvention with a base polymer, the molecular weight of the starting basepolymer may decrease.

In a further embodiment of the invention, the gas barrier enhancingadditives of the invention may be blended with other physical propertyimproving additives known in the art i.e., mechanical propertiesimproving additives such as creep control agents, impact strengthadditives, flow control additives, melt flow control additives and thelike.

In a further embodiment the invention also provides a containercomprising a polyester composition comprising a polyester; a mechanicalproperty improving agent; and a gas barrier enhancing additive comprisesa compound having the chemical structure of Formula II:

wherein X and X₆, independent of one another, comprise hydrogen, halide,heteroatom, hydroxyl, amino, amido, alkylamino, arylamino, alkoxy,aryloxy, nitro, acyl, cyano, sulfo, sulfato, mercapto, imino, sulfonyl,sulfenyl, sulfinyl, sulfamoyl, phosphonyl, phosphinyl, phosphoryl,phosphino, thioester, thioether, anhydride, oximino, hydrazino,carbamyl, phosphonic acid, phosphonato, or a C₁-C₁₀ monovalenthydrocarbon which is unsubstituted or substituted with one or morefunctional moieties; wherein X₁, X₂, X₃, X₄, and X₅, independent of oneanother, comprise a heteroatom or a C₁-C₁₀ divalent hydrocarbon, whereineach heteroatom or C₁-C₁₀ divalent hydrocarbon is unsubstituted orsubstituted with one or more functional moieties or one or more C₁-C₁₀hydrocarbyls that are unsubstituted or substituted with one or morefunctional moieties; and wherein s, t, u, and v, independent of oneanother, is a number from 0 to 10; wherein when X₃ comprises a C₆ or C₁₀divalent aromatic hydrocarbon, X and X₆, independent of one another,comprise a hydrogen, halide, heteroatom, hydroxyl, amino, amido,alkylamino, arylamino, alkoxy, aryloxy, nitro, acyl, cyano, sulfo,sulfato, mercapto, imino, sulfonyl, sulfenyl, sulfinyl, sulfamoyl,phosphonyl, phosphinyl, phosphoryl, phosphino, thioester, thioether,anhydride, oximno, hydrazino, carbamyl, phosphonic acid, phosphonato, ora C₃-C₁₀ monovalent cyclic or heterocyclic non-aryl hydrocarbon that areunsubstituted or substituted with one or more functional moieties.

EXAMPLES

The present invention is illustrated by the following Examples, butshould not be construed to be limited thereto. In the Examples, eachreactant is specified in grams and moles unless specified otherwise.

Example 1 Condensation Product of Terephthalic Acid and 2-phenoxyethanol

398.0 grams of purified terephthalic acid (2.4 moles) and 732.0 grams of2-phenoxyethanol (5.3 moles) were charged to a 2 liter round bottomflask equipped with a mechanical stirrer, inert gas inlet, andthermocouple. A packed partial condenser, wrapped with heat tape wasplaced between the cold condenser and water trap. The packed partialcondenser was then heated to 120° C., 0.1 wt. % of hypophosphorous acidwas added as a color stabilizer and the reaction mixture was heated to245-250° C. at which time the 2-phenoxyethanol began refluxing. Theslurry of terephthalic acid and 2-phenoxyethanol was maintained between245-250° C. for 24 hr at which time the reaction mixture was clear. GCanalysis of the reaction mixture showed 99.4% diester and 0.6%monoester. The excess 2-phenoxyethanol was then stripped under vacuumuntil none was detected by GC analysis. The reaction mixture was cooledto 120° C. and then decanted to yield 1015.0 g of diester as a whitesolid.

Example 2 Condensation Product of Isophthalic Acid and 2-phenoxyethanol

398.0 grams of purified isophthalic acid (2.4 moles) and 732.0 grams of2-phenoxyethanol (5.3 moles) were charged to a 2 liter round bottomflask equipped with a mechanical stirrer, inert gas inlet, andthermocouple. A packed partial condenser, wrapped with heat tape wasplaced between the cold condenser and water trap. The packed partialcondenser was then heated to 120° C., 0.1 wt. % of hypophosphorous acidwas added as a color stabilizer, and the reaction mixture was heated to245-250° C. at which time the 2-phenoxyethanol began refluxing. Theslurry of terephthalic acid and 2-phenoxyethanol was maintained between245-250° for 24 hr at which time the reaction mixture was clear. GCanalysis of the reaction mixture showed 99.4% diester and 0.6%monoester. The excess 2-phenoxyethanol was then stripped under vacuumuntil none was detected by GC analysis. The reaction mixture was cooledto 120° C. and then decanted to yield 1010.0 g of diester as a whitesolid.

Example 3 Condensation Product of 2,6-naphthalene Dicarboxylic Acid with2-phenoxyethanol

519.0 grams of 2,6-naphthalenedicarboxylic acid (2.4 moles) and 732.0grams of 2-phenoxyethanol (5.3 moles) were charged to a 2 liter roundbottom flask equipped with a mechanical stirrer, inert gas inlet, andthermocouple. A packed partial condenser, wrapped with heat tape wasplaced between the cold condenser and water trap. The packed partialcondenser was then heated to 120° C., 0.1 wt. % of hypophosphorous acidwas added as a color stabilizer, and the reaction mixture was heated to245-250° C. at which time the 2-phenoxyethanol began refluxing. Theslurry of terephthalic acid and 2-phenoxyethanol was maintained between245-250° C. for 24 hr at which time the reaction mixture was clear. GCanalysis of the reaction mixture showed 99.4% diester and 0.6%monoester. The excess 2-phenoxyethanol was then stripped under vacuumuntil none was detected by GC analysis. The reaction mixture was cooledto 120° C. and then decanted to yield 1150.0 g of diester as a whitesolid.

Example 4 Condensation Product of Terephthalic Acid and 2-phenoxyethanol

1,592.0 grams of purified terephthalic acid (9.6 moles) and 2,928.0grams of 2-phenoxyethanol (21.2 moles) were charged to a 10 liter roundbottom flask equipped with a mechanical stirrer, inert gas inlet, andthermocouple. A packed partial condenser, wrapped with heat tape wasplaced between the cold condenser and water trap. The packed partialcondenser was then heated to 120° C., 0.4 wt. % of hypophosphorous acidwas added as a color stabilizer and the reaction mixture was heated to245-250° C. at which time the 2-phenoxyethanol began refluxing. Theslurry of terephthalic acid and 2-phenoxyethanol was maintained between245-250° C. for 24 hr at which time the reaction mixture was clear. GCanalysis of the reaction mixture showed 99.4% diester and 0.6%monoester. The excess 2-phenoxyethanol was then stripped under vacuumuntil none was detected by GC analysis. The reaction mixture was cooledto 120° C. and then decanted to yield 4,060.0 g of diester as a whitesolid.

Example 5 Condensation Product of Phthalic Acid and 2-phenoxyethanol

398.0 grams of purified phthalic acid (2.4 moles) and 732.0 grams of2-phenoxyethanol (5.3 moles) were charged to a 2 liter round bottomflask equipped with a mechanical stirrer, inert gas inlet, andthermocouple. A packed partial condenser, wrapped with heat tape wasplaced between the cold condenser and water trap. The packed partialcondenser was then heated to 120° C., 0.1 wt. % of hypophosphorous acidwas added as a color stabilizer, and the reaction mixture was heated to245-250° C. at which time the 2-phenoxyethanol began refluxing. Theslurry of terephthalic acid and 2-phenoxyethanol was maintained between245-250° for 24 hr at which time the reaction mixture was clear. GCanalysis of the reaction mixture showed 99.4% diester and 0.6%monoester. The excess 2-phenoxyethanol was then stripped under vacuumuntil none was detected by GC analysis. The reaction mixture was cooledto 120° C. and then decanted to yield 1010.0 g of diester as a whitesolid.

Example 6 Condensation Product of Terephthalic Acid and 2-phenoxyethanol

796.0 grams of purified terephthalic acid (4.8 moles) and 1,464.0 gramsof 2-phenoxyethanol (10.6 moles) were charged to a 5 liter round bottomflask equipped with a mechanical stirrer, inert gas inlet, andthermocouple. A packed partial condenser, wrapped with heat tape wasplaced between the cold condenser and water trap. The packed partialcondenser was then heated to 120° C., 0.2 wt. % of hypophosphorous acidwas added as a color stabilizer and the reaction mixture was heated to245-250° C. at which time the 2-phenoxyethanol began refluxing. Theslurry of terephthalic acid and 2-phenoxyethanol was maintained between245-250° C. for 24 hr at which time the reaction mixture was clear. GCanalysis of the reaction mixture showed 99.4% diester and 0.6%monoester. The excess 2-phenoxyethanol was then stripped under vacuumuntil none was detected by GC analysis. The reaction mixture was cooledto 120° C. and then decanted to yield 2,030.0 g of diester as a whitesolid.

Example 7

A polyester composition was prepared by blending a ground 1103 Apolyester resin (Invista, Spartanburg, S.C.) with either 3, 4 or 5 wt %of PEM, a gas barrier additive having the chemical formula:

The polyester composition was injection molded using conventionalmethods to obtain a container preform. The container preforms appearedto be of good quality in terms of clarity and shape without anyindication of buildup on the core pin or in the thread splits and otherparts of the injection molder, indicating there was no substantialplate-out on the injection molding equipment. The container preformsthen were stretch blow molded using conventional methods to obtainbottles which were clear, colorless to the eye, and indistinguishablefrom one another.

Although the present invention has been described with reference tospecific details of certain embodiments thereof, it is not intended thatsuch detail should be regarded as limitations upon the scope of theinvention, except as and to the extent that they are included in theaccompanying claims.

1. A composition containing 99.4% of a diester of the formula:

and 0.6% of a monoester having the formula

wherein Ar is aryl; Ar′ is aryl; R is an alkylene radical having 2-20carbon atoms; n=1-20.
 2. A composition according to claim 1, whereinsaid aryl group is selected from the group consisting of phenyl,naphthyl, biphenyl, terphenyl, and all positional isomeric derivativesthereof. 3-7. (canceled)
 8. A composition according to claim 2, whereinsaid diester has the formula

and said monoester has the formula


9. A composition according to claim 2, wherein said diester has theformula

and said monoester has the formula


10. A composition according to claim 2, wherein said diester has theformula

and said monoester has the formula


11. A composition according to claim 2, wherein said diester has theformula

and said monoester has the formula


12. A composition according to claim 2, wherein said diester has theformula

and said monoester has the formula